JP6970542B2 - Coating composition for forming water- and oil-repellent film and water- and oil-repellent film - Google Patents

Description

The present invention relates to a coating composition for forming a water-repellent and oil-repellent film that does not contain fluorine and can exhibit water-repellent and oil-repellent properties, and a water- and oil-repellent film.

So far, in order to exhibit water repellency and oil repellency, introduction of a functional group containing fluorine such as a fluoroalkyl group has been generally performed. According to Patent Document 1, silsesquioxane containing a fluoroalkyl group is disclosed to be effective as a surface treatment agent having excellent water and oil repellency. Further, according to Patent Document 2, a polymerizable compound having a pentafluorosulfanil group is disclosed as a compound capable of imparting water and oil repellency.
Studies on water-repellent and oil-repellent properties that do not contain fluorine have also been conducted. For example, according to Patent Document 3, it is disclosed that water- and oil-repellent properties can be imparted by introducing a long-chain hydrocarbon such as an octadecyl group. There is.
Further, the present inventors have filed a patent application for Patent Document 4 regarding a fluorine-free water-repellent oil-repellent film, and a patent application for Patent Document 5 regarding a coating composition for forming a fluorine-free water-repellent oil-repellent film. There is.

Japanese Unexamined Patent Publication No. 2012-1724. Japanese Unexamined Patent Publication No. 2010-22279 Japanese Unexamined Patent Publication No. 2011-148718 Japanese Unexamined Patent Publication No. 2015-44983 Japanese Unexamined Patent Publication No. 2016-30763

The application of a functional group containing fluorine is the most effective for developing water repellency and oil repellency, but the decomposition of the water-repellent oil-repellent film containing fluorine and the diffusion of fluorine into the environment during disposal have become problems, and the fluorine is contained. There is a need to develop non-water- and oil-repellent materials.
The present inventors have filed patent applications for water-repellent and oil-repellent materials according to Patent Documents 4 and 5, but higher-performance water- and oil-repellent materials, particularly water-repellent materials that exhibit high oil-repellent performance. Oil repellent materials are required.

The water- and oil-repellent material of the present invention is a water- and oil-repellent material capable of exhibiting excellent water and oil repellency without containing fluorine atoms that contribute to environmental pollution, and has the following features. It is a water- and oil-repellent material.

[1] A coating composition for forming a water- and oil-repellent film, which comprises a compound having a plurality of isocyanate groups, a modified silicone compound having a plurality of functional groups reacting with the isocyanate group, polyethylene glycol and a cross-linking agent.
[2] The coating composition for forming a water-repellent oil-repellent film according to the above [1], wherein the modified silicone compound contains a both-terminal hydroxyl-modified silicone compound as a main component and further contains both-terminal amine-modified silicone compounds. thing.
[3] A cured product of the coating composition for forming a water-repellent oil-repellent film according to the above [1] or [2], wherein the hydrophilic domain is dispersed and present on the outermost surface of the water-repellent domain. A water- and oil-repellent film characterized by being made.

The fluorine-free water-repellent and oil-repellent material obtained in the present invention is a material having a very small environmental load because it does not contain fluorine. In addition, it was possible to improve the water-repellent and oil-repellent properties that could not be obtained in the past, and to maintain particularly high water-repellent performance and realize higher oil-repellent performance.

The coating composition for forming a water- and oil-repellent film of the present invention is characterized by containing a compound having a plurality of isocyanate groups, a modified silicone compound having a plurality of functional groups reacting with an isocyanate group, polyethylene glycol and a cross-linking agent. ..

Examples of the compound having a plurality of isocyanate groups include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H-XDI), and xylylene diisocyanate (XDI). ), Hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMHMDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatemethyl) cyclohexane (H6XDI), 1,5-naphthalenediisocyanate, dicyclohexyldiisocyanate (H12MDI) and the like can be mentioned. These isocyanate compounds may be used alone or in combination of two or more, or may be used as a prepolymer of an adduct, a burette, or an isocyanurate.

The modified silicone compound having a plurality of functional groups that reacts with the isocyanate group may be any compound having a plurality of functional groups at the linear end or the end of the side chain of the silicone, but is preferably modified with hydroxyl groups at both ends. Examples thereof include silicone compounds and both-terminal amine-modified silicone compounds.

As the polyethylene glycol, commercially available polyethylene glycol having various molecular weights can be used. Among them, it is preferable to use polyethylene glycol having an average molecular weight of about 200 to 4000.

The cross-linking agent may be any compound having an isocyanate group, the modified silicone compound and a compound having a group reacting with polyethylene glycol, and a compound having an epoxy group is particularly preferable.

The coating composition for forming a water-repellent oil-repellent film of the present invention contains the compound having an isocyanate group, the modified silicone compound, the polyethylene glycol and the cross-linking agent in the composition in order to form the water-repellent oil-repellent film. However, the compound having an isocyanate group reacts with the modified silicone compound, the polyethylene glycol and the cross-linking agent, respectively, and the cross-linking agent reacts with the modified silicone compound and the polyethylene glycol.

The ratio of each component constituting the coating composition for forming a water- and oil-repellent film is preferably mixed as follows.
_{The total amount of the hydroxyl group (-OH) and amino group (-NH 2} ) of the modified silicone compound and the polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is {(-OH) + (-) in an equivalent ratio. NH ₂ )} / (-NCO) = 2 to 20, preferably 2 to 11, and the modified silicone compound is relative to the total of the modified silicone compound and the polyethylene glycol. It is preferable to mix the mixture in the range of 2 to 10% by weight.

The cross-linking agent is 3 to 15% by weight, preferably 4 to 10% by weight, based on the total weight of the compound having a plurality of isocyanate groups, the modified silicone compound having a plurality of functional groups reacting with the isocyanate groups, polyethylene glycol and the cross-linking agent. Add at a rate of%.

Further, even if a curing catalyst or a reaction initiator for accelerating the reaction of the compound in the coating composition for forming a water-repellent oil-repellent film is added to the coating composition for forming a water-repellent oil-repellent film of the present invention. good.

As the curing catalyst, known curing catalysts can be widely used, and there are no particular restrictions, but examples thereof include organometallic compounds and tertiary amines, and in particular, organotin catalysts, organotitanium catalysts, and organic zirconium. It is preferable to use a compound catalyst. Examples of the organic metal compound include stanus diacetate, stanus dioctate, stanus dilaurate, stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, and the like. Nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, zirconium tetraacetylacetonate, zirconiumtetraacetylacetonate, titanium diisopropoxybis (ethylacetacetate), zirconium dibutoxybis (ethylacetate) Acetate) and the like. These can be used alone or in combination of two or more. The amount of the curing catalyst used is not particularly limited, but is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the compound having an isocyanate group.

The reaction initiator is selected from a cationic polymerization initiator and a radical polymerization initiator, but it is preferable to use a cationic polymerization initiator. As the cationic polymerization initiator, a known cationic polymerization initiator can be widely used.
The amount of the reaction initiator used is not particularly limited, but is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the cross-linking agent.

Examples of commercially available cation initiators include, for example, Adeka Opton CP77, Adeka Opton CP66 (above, manufactured by ADEKA Corporation), "CI-2339", and "CI-2624" (above, manufactured by Nippon Soda Corporation). ), "Sun Aid SI-45", "Sun Aid SI-60L", "Sun Aid SI-80L", "Sun Aid SI-100L" (all manufactured by Sanshin Chemical Industry Co., Ltd.), Irgacure 250 (Ciba Specialty Chemicals) Co., Ltd.) and the like. These can be used alone or in combination of two or more.

When the coating composition for forming a water-repellent oil-repellent film of the present invention is a liquid, the coating liquid for forming a water-repellent oil-repellent film is appropriately referred to as "coating liquid of the present invention" as it is or by diluting with a solvent. Can be used as.
When the coating composition for forming a water-repellent oil-repellent film of the present invention is a solid or a highly viscous liquid, it can be dissolved in a solvent and used as a coating liquid for forming a water-repellent oil-repellent film. The concentration of the solution of the coating composition for forming a water-repellent oil-repellent film of the present invention is preferably about 1 wt% to 90 wt% when a thin film of the water-repellent oil-repellent film is produced.

Examples of the solvent include acetone, chloroform, ethanol, isopropanol, methanol, toluene, tetrahydrofuran (THF), water, benzene, benzyl alcohol, 1,4-dioxane, propanol, carbon tetrachloride, cyclohexane, cyclohexanone, methylene chloride, phenol, and the like. Pyridine, trichloroethane, acetic acid, ethyl acetate, butyl acetate, N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, dimethylcarbonate, acetonitrile, N- Methylmorpholine-N-oxide, butylene carbonate, 1,4-butylolactone, diethyl carbonate, diethyl ether, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dioxolane, ethylmethylcarbonate , Methylformate, 3-methyloxazolidin-2-one, methylpropionate, 2-methyltetratetra, sulfolane can be used.

The coating liquid of the present invention is obtained by mixing the above-mentioned coating composition for forming a water- and oil-repellent film, dissolving it in a solvent in some cases, and then stirring it. Although stirring can be performed at room temperature, it takes a long time, so it is preferable to heat the mixture to 40 ° C to 80 ° C.
The stirring time varies depending on the combination of temperature and composition, but is usually about 1 hour or more and 24 hours when heated to 40 to 60 ° C. It is preferably 3 to 24 hours. If the time is short, the water- and oil-repellent effect cannot be sufficiently obtained because the domain matrix formation of the hydrophilic domain and the water-repellent matrix described later is insufficient. Further, if the time is too long, the domain matrix shape becomes too large, and a phase-separated structure of the hydrophilic domain having a water-repellent and oil-repellent effect and the water-repellent matrix cannot be obtained.

The water- and oil-repellent film of the present invention is formed by applying the coating liquid of the present invention on a substrate, and the above-mentioned compound group is dispersed in a phase of a hydrophilic domain and a water-repellent domain by self-assembly. ..
Self-organization is the natural assembly of relatively small molecules to build higher-order structures. For example, crystals, micelles, monolayers, mesoporous structuring and the like can be mentioned. The phases formed by the self-assembly of the present invention are the hydrophilic domain and the water repellent domain.

In the present invention, the coating liquid of the present invention is applied onto a substrate to form a phase-separated structure due to the difference in polarity. At this time, a water- and oil-repellent film can be formed by curing the compound in the coating liquid.
That is, the water-repellent oil-repellent film of the present invention is a cured product of the coating composition for forming the water-repellent oil-repellent film according to the above [1] or [2], and the hydrophilic domain is the most water-repellent domain. It is characterized by being dispersed and present on the surface.

The water- and oil-repellent membrane of the present invention does not contain a fluorine-containing functional group, and the structure in which hydrophilic domains are dispersed in the water-repellent domain exceeds the oil-repellent properties that can be achieved with only a single substance. It develops water and oil repellency.

The water- and oil-repellent film of the present invention exhibits its characteristics by forming a structure in which the hydrophilic domain is dispersed in the water-repellent domain on the outermost surface. Further, it is preferable that the composition ratio and shape of the hydrophilicity and water repellency of the outermost surface satisfy the morphology described later.

That is, the water- and oil-repellent film of the present invention preferably has a hydrophilic domain area of 20 to 70% on the film surface. If it is less than 20%, the desired oil repellency cannot be obtained. If it exceeds 70%, the hydrophilicity becomes high and the desired water repellency cannot be exhibited. It is preferably 30 to 60%.

The areas of the hydrophilic domain and the water-repellent domain in the present invention are measured by the phase mode measurement of the scanning probe microscope and are measured by the different phases of the data. (Water repellent when the phase difference is small, hydrophilic when the phase difference is large). That is, after imaging the states having different phases, the hydrophilic domain area ratio can be calculated from the area ratios of the different phase images.

The shape of the hydrophilic domain of the present invention is not particularly limited. The shape of the hydrophilic domain is formed by self-organization by phase separation, and takes the shape of particles (spherical, elliptical spherical and its deformed shape), fibrous and the like. The size of the hydrophilic domain is preferably 5 to 100 nm. If it is less than 5 nm, the desired oil repellency cannot be obtained. If it exceeds 100 nm, the hydrophilicity becomes high and the desired water repellency cannot be exhibited. It is preferably 8 to 50 nm.

As the hydrophilic domain, a group having a hydrophilic polarity having an effect of increasing the surface free energy and a group having a polar group bonded by a reaction are collected. Examples of the polar group include an isocyanate group, a hydroxyl group, an amino group, a (meth) acloyl group, an epoxy group, a thiol group, a carboxyl group, an acid anhydride-modified group and a cyano group, and the polar group is formed by the reaction. Examples of the bonded group include an amide bond, a urethane bond, a urea bond, a peptide bond, an ether bond, an ester bond, a sulfide bond, a thioester bond and the like.

The water-repellent domain is a collection of non-polar groups having low polarity and having an effect of reducing the surface free energy and those to which non-polar groups are bonded by a reaction. Examples of the group having a non-polar group include a vinyl group, an aliphatic hydrocarbon group (alkyl group, cycloalkyl group, alkenyl group, alkenylene group, alkoxy group, adamantyl group), and aromatic hydrocarbon group (aryl group, aralkyl group). Group, arylene group), and examples of the non-polar group bonded by the reaction include carbon-silicon bond, siloxane bond, alkane, cycloalkane and the like.
These form a domain alone or in combination of two or more.

The water- and oil-repellent film of the present invention is characterized in that the hydrophilic domain is dispersed in the water-repellent domain, and is produced by mixing the hydrophilic composition with the water-repellent composition at the ratio described later. Is possible. The mixing ratio of the hydrophilic composition may be 50% or less with respect to the water-repellent composition, but it is necessary to mix at least so that the area of the hydrophilic domain is 2% or more on the surface of the water-repellent oil-repellent film. There is.

The coating liquid of the present invention can be applied to an object to be treated by a conventionally known method. The coating liquid of the present invention may be directly applied to the substrate by a known method such as dip coating, spray coating, foam coating, etc., or may be cured and fixed by heating, ultraviolet irradiation, or the like after coating. Alternatively, the coating composition for forming a water- and oil-repellent film is dispersed in an organic solvent or water and diluted to obtain a coating liquid, which is then applied to the surface of the substrate by a known method, dried, heated, irradiated with ultraviolet rays, or the like. It may be cured and fixed by. Preferably, an appropriate cross-linking agent is added to the coating liquid of the present invention, mixed, coated on the surface of the substrate by a known method, and then cured and solidified.

By adding a cross-linking agent to the coating liquid for forming a water-repellent oil-repellent film of the present invention and cross-linking, a three-dimensional network structure is constructed and mechanical properties and heat resistance are improved. Further, the coating liquid for forming a water- and oil-repellent film of the present invention is provided with other functional components such as ultraviolet absorbers, heat-resistant absorbents, antibacterial agents, antistatic agents, paint fixing agents, and pigments and dyes for coloring. It can also be added and used in combination.

Examples of the present invention will be specifically described, but the examples do not limit the present invention. ("Parts" means "parts by weight" and "%" means "% by weight".)

<Preparation of thermosetting composition solution>
[Example 1]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 12 parts of both-terminal hydroxyl-modified polysiloxane (1,3-Biz (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and both-terminal amine-modified polysiloxane 0. Mix 4 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.). Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 26 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), thermal initiator 0.8 Parts (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, and the mixture was stirred at 50 ° C. for 3 hours. Then, 237 parts of polyethylene glycol (PEG # 400: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 4 equivalents.

[Example 2]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 19 parts of both-terminal hydroxyl-modified polysiloxane (1,3-Bis (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and both-terminal amine-modified polysiloxane 0. Mix 6 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.). Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 35 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), thermal initiator 1.1 Parts (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, and the mixture was stirred at 50 ° C. for 3 hours. Then, 356 parts of polyethylene glycol (PEG # 400: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 6 equivalents.

[Example 3]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 31 parts of both-terminal hydroxyl-modified polysiloxane (1,3-Bis (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and both-terminal amine-modified polysiloxane 0. 9 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 55 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), heat initiator 1.7 Part (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) was mixed, dissolved in a THF solution to 20%, and stirred at 50 ° C. for 24 hours. Then, 593 parts of polyethylene glycol (PEG # 400: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 10 equivalents.

[Example 4]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 37 parts of both-terminal hydroxyl-modified polysiloxane (1,3-Biz (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and both-terminal amine-modified polysiloxane 1. 1 part (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed. Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 35 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), thermal initiator 1.1 Parts (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, and the mixture was stirred at 50 ° C. for 5 hours. Then, 330 parts of polyethylene glycol (PEG # 400: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 6 equivalents.

[Example 5]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 8 parts of both-terminal hydroxyl-modified polysiloxane (1,3-Bis (4-hydroxybutyl) ttramethyldisiloxane: manufactured by Tokyo Chemical Industry) and both-terminal amine-modified polysiloxane 0. Mix 2 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.). Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 36 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), thermal initiator 1.1 Parts (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, and the mixture was stirred at 50 ° C. for 5 hours. Then, 372 parts of polyethylene glycol (PEG # 400: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 6 equivalents.

[Example 6]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 61 parts of hydroxyl-terminated polysiloxane at both ends (1,3-Biz (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and amine-modified polysiloxane at both ends 1. 9 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 54 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), heat initiator 1.6 Parts (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, and the mixture was stirred at 50 ° C. for 5 hours. Then, 550 parts of polyethylene glycol (PEG # 400: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 10 equivalents.

[Example 7]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 13 parts of hydroxyl-terminated polysiloxane at both ends (1,3-Biz (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and amine-modified polysiloxane at both ends 0. Mix 4 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.). Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 56 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), heat initiator 1.7 Parts (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, and the mixture was stirred at 50 ° C. for 5 hours. Then, 620 parts of polyethylene glycol (PEG # 400: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 10 equivalents.

[Example 8]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 19 parts of both-terminal hydroxyl-modified polysiloxane (1,3-Bis (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and both-terminal amine-modified polysiloxane 0. Mix 6 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.). Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 35 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), thermal initiator 1.1 Parts (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, and the mixture was stirred at 50 ° C. for 3 hours. Then, 356 parts of polyethylene glycol (PEG # 400: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 2.7 equivalents.

[Example 9]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 66 parts of both-terminal hydroxyl-modified polysiloxane (1,3-Biz (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and both-terminal amine-modified polysiloxane 1. 98 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 109 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), thermal initiator 3.3 Parts (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, and the mixture was stirred at 50 ° C. for 5 hours. Then, 1248 parts of polyethylene glycol (PEG # 4000: manufactured by Nacalai Tesque) was added to prepare a thermosetting composition solution.
In this solution, the total amount of the hydroxyl group (-OH) and amino group (-NH2) of the modified silicone compound and polyethylene glycol with respect to the isocyanate group (-NCO) of the compound having an isocyanate group is the equivalent ratio [{(-OH) + ( -NH2)} / (-NCO)] corresponds to about 4 equivalents.

[Comparative Example 1]
100 parts of isocyanate compound (D-101: manufactured by Mitsui Chemicals Polyurethane), 49 parts of hydroxyl-terminated polysiloxane at both ends (1,3-Biz (4-hydroxybutyl) tetramethyldisiloxane: manufactured by Tokyo Chemical Industry) and amine-modified polysiloxane at both ends 1. Mix 5 parts (KF-8010: manufactured by Shin-Etsu Chemical Co., Ltd.). Next, curing catalyst: 0.8 part of tetravalent tin compound (No. 918: manufactured by Sanko Machinery Co., Ltd.) and cross-linking component: 10 parts of Novorak resin (YDCN-700-2: manufactured by Toto Kasei), heat initiator 0.3 Part (Sun Aid SI-60L: manufactured by Sanshin Chemical Industry Co., Ltd.) was mixed, dissolved in a THF solution so that the total amount of the solute containing polyethylene glycol added later was 20%, stirred at 50 ° C. for 4 hours, and then thermosetting. The composition solution was used.

<Making a film-like cured product>
The thermosetting composition solutions obtained in Examples 1 to 8 and Comparative Example 1 were cast on a silicon wafer substrate and heat-cured at 180 ° C. for 4 hours to obtain a transparent film-like cured product having a thickness of 2 μm. ..

<Evaluation of water and oil repellency of film-like cured products>
The contact angles of the film-like cured products obtained in Examples 1 to 8 and Comparative Example 1 were measured by a contact angle meter (Drop Master manufactured by Kyowa Interface Science Co., Ltd., analysis software FAMAS). Oleic acid (OA) and n-hexadecane (HD) were used for the evaluation of oil repellency, and distilled water (DW) was used for evaluation of water repellency. The dropping amount was 2 μL, and the contact angle 1 second after the measuring solution was dropped on the membrane was measured. The results are shown in Table 1.

In Examples 1 to 3, an OA contact angle of 100 ° or more was obtained. It can be seen that the excessive addition of PEG has excellent oil repellency, as compared with the low OA contact angle of Comparative Example 1 in which PEG was not added.
Since the OA contact angle of 100 ° or more was obtained in Examples 4 to 7 and the OA contact angle of Comparative Example 1 to which the hydrophilic component was not added was low, the one having a large ratio of the hydrophilic component to the hydrophobic component was more oil repellent. It turns out that it has.
In Example 8, the contact angle of oleic acid was 100 ° or more. It can be seen that even if the molecular weight of PEG is 1000, it has excellent oil repellency as well as 400.
Further, in Examples 2 and 9, it was confirmed that the n-hexadecane contact angles were 49 ° and 59 °, which were larger values than 39 ° shown in Comparative Example 1.
As shown above, the coating composition for forming a water- and oil-repellent film of the present invention has a large contact angle with oleic acid and n-hexadecane while maintaining water repellency, which was not possible with conventional fluorine-free materials, in other words. It was possible to obtain oil-repellent properties.

The fluorine-free water- and oil-repellent material of the present invention has properties such as transparency, stain resistance, water- and oil-repellent properties, surface slipperiness, scratch resistance and heat resistance, and is used for optical fiber sheath materials and glass filters. In addition to being suitable for various applications that require heat resistance and wear resistance, such as protective films, optical materials such as solar cells, glass top stoves, top plates for IH heaters, and sliding surface treatment films, for cosmetics. It is also suitable for applications.

Claims (2)

A coating composition for forming a water-repellent oil-repellent film , which comprises a compound having a plurality of isocyanate groups, a modified silicone compound having a plurality of functional groups reacting with the isocyanate group, polyethylene glycol and a cross-linking agent.
The modified silicone compound contains a terminal hydroxyl group-modified silicone compound as a main component and further contains both terminal amine-modified silicone compounds.
The hydroxyl group-modified silicone compound is 8 to 66 parts by mass, the both-terminal amine-modified silicone compound is 0.2 to 1.98 parts by mass, and the polyethylene glycol is 237 to 1248 parts by mass with respect to 100 parts by mass of the compound having an isocyanate group. A coating composition for forming a water- and oil-repellent film , which comprises 26 to 109 parts by mass and a cross-linking agent. A cured product of the coating composition for forming a water-repellent oil-repellent film according to claim 1, wherein the hydrophilic domains are dispersed and present on the outermost surface of the water-repellent domain. Oil repellent film.